Polymerization of olefines



June 29, 1937. M. DE slM ET A1.

lPQLYMERIZATION OF OLEFINES Filed July 12, 19:55

2 Sheets-Sheet 1 June 29, 1937.

M. DE slM ET Ax.

POLYMERIZATION OF OLEFINES Filed July 12, 1955 2 Sheets-Sheet 2 /ja/renf /a/ mer UNITED STATES PATENT oFl-lE f 'laoss,524" L Q- l PoLYMEm-ZATION oF oLEFINEs l Martin de 's imana Freaerieknnilmer, nerime ley, Calif., signers to shell Development Company, VSan Francisco, Califsa corporation Appleatien ,July 12, 1935, seal No. eine 'Y l Claims. `(ol,Y 266.'.2). Our invention relates to the polymerization@ olenes, under the catalytic. action of polymerizing catalysts particularly'tho'se ofthe type ofv boron fluoride, such as aluminum chloride, zinc chloride.`

l:' ept `in solutions of anfinertrfdiluent, to I lreve'lit"4 unduethickenng ofthe product, of the' reaction, I

which might prevent thelpolyme'rization fromV going to substantial completion@ Duringv the polymerization'considerable heat'deboron iluoride, we havefound that extremely large Y 5 yetc@ In particular itis concerned with the`poly' 'velops; It'has been-recognized Ain the past, that 5 meriza'tion. of propylene and/ orbeta-iso-olenesj rit' isessential to keep'the temperature'throughout underthe vinfluence vofaV gaseous polymerization the reacting mass -w'ithin certaindimitslfFor catalyst of thetype of boron iluoride, which-may instancepin the case of polymerizing'iso-butylene include hydrogen xiiuoride, said betafiso-olenes by "means, of boron uoride thel temperature lohayingless than 9 carbon'atoms per molecule and'- hollld be kept bl0W10C-,19I1d it has been. 10 having the general formulaI suggested to add solid vcarbon dioxide to the rev RI `acting mass 4 to maintain an evenly low temperafture.' Y' l CHFZC\ v We hav'e found,howeyer,.that very often cooling r f l v Rl Withsolid carbon dioxide or external coolingisinf 15 i whereinR1 and R2 represent alkylradicals and of sufficient .and 'doeenot I eoo! ,to the forme'tionvof. which is, buty1ene f polymers Vof molecular sizessuiiclently large for i CH, y many purposes.. Solid carbon dioxideis notsol- CH C ublev in the. reaction mass, and its effect is that t I of cooling parts of the mixture to temperatures 20 .l y CB: `as low as-80v"C., and allowing at the-same timev 1.15 the rst member i lfthe temperature Vin other'parts to rise to above The catalysts which we intend to' use in our *loeCf-at any Onermoment 0f the Pelymerzetiepl process'may be termed low'temperaturecatalysts.''" Therese isem uneYen polymeizeftlone f f Y They include all those which promote 'DOlymerizaf Ommvention' comprises improved methods. 2'5 'tion of olenes materially at o'r below atmospheric V l Cooling, Which depend 01`- their Successful exeel ltemperature. Thus in this class are vcontained tion *0n the immediate and even .remove-lef the .boronlfluoride hydrogen fluoride, aluminum' chlor heet efvepolymerzaon and themaintenanoe of a' v 'ride, v'zinc chloride and iron chloride. Excluded desired Teeeton temperature- With narrow are suchV catalysts as sulfuric acid, phosphoric one Sueh'meehedeoneistsef mixing With the 01e' 30` "acdfoxygen, cyanides, etc. fines-or a solution thereof a' cooling liquid miscible Y The' gaseouscatalysts'boron fluoride and hydroe therewith adhaving a boiling temperature not gen-iluoride or mixtures thereof are particularly exceeding the'of the desredeaction temperature useful; because they not only Aproducecertain undelfpevailng.Pressure$ the Polymeriza- 'types lof' highly valuable polymers; but they .lend Ytien? takes Place 'end the heatef ,reaction S de'" 35 themselves exceptionally well to continuous meth- Veloped at leest Perf' 0f the cooling liquid eVePO" "Casa-:polymerization -v H L y. rates, therelzly' absorbing heat.l Becau'seof thev none object of om. process to provd means complete Vmiscibility of the cooling liquid andthe f0'1 accurately wml-011mg the temperature of zrevolelines', coolingis notV only distributed evenly but 40 action,` the temperature control Abeing oneof'the u 'ii-1501s efefeeiVe-mmedatel Theese no( delay' 40 `prime factors in obtaining uniform products, and e. QI 'rise 0fA temprature involved during-'Which itfisv another object to provide a continuous l, fermatin' 0f*relatively Small and' undesirable method for manufacturing polymers. DOlYmelS can' take Place- Wl? p leferto 11S@ the appearancefrom highly viscous liquids to rubb'e'rditions of reaction corresponds substantially to 45 like' materials, dependingppon the secic 60mn.. the desired reaction temperature. 'This permits tionsnnder which they aremanufactured. They the use 0f any quantity 0f C001ing liquid in eXCeSS aresolnble or--dispersablein hydrocarbon 011s and of the minimum required toehold the temperacanlbefusedfor plasticizers or'lconstituents of ture 'at the DIOPGI' leVel. Wlout nVOlVDg the Yli0.la.cquers or lubricating oilsyetev-v f risk of coolingxto too low a temperature, which 50 Ithas been :the'pi'actce heretofore to'carry out might unnecessarily retard the :reactionVV andere-V -the polymerization-of Voleflnes with suitable cata@ S1111; inlmdesilable Productsl ly'sts' by bringing vthe catalystln-'contact with the f r*lllhen polymerlzlng propylene and beta-'iso-oleliquid'reactant.-'1'he oleflnes were preferably .fines in' contact with, a catalyst ofthe type of 55 polymers' are formed if the polymerizationstemperature is kept within the range of C, to 80 C. the exact optimum temperature depending upon -various factors involved in the polymerization. It must be understood, however, that in order ito, obtain a uniformproduct, the temperature during an individual run requires control within much closer limits, preferably within 10 C.

In our preferred procedure we mix the olenes, or a solution thereof with an inert liquid whose average boiling temperature lies somewhere between 100'C. and 20b C.,` and whose boiling range is preferably not more than about 25 C. lIt shall be understood, however, that in some cases liquids may be .used of a wider boiling range. such as natural gasoline, or bottled gas, which ymay possess boiling ranges as high as 200 C. but which are sufilciently volatile, vso that substantial portions thereof evaporate causingthe desired cooling. 1

Occasionally it is practical to apply pressures above or'below atmospheri'cinthe reaction zone in order to adjust the boilingpoi-nt of a particularly suitable cooling liquid. For example, if it is attempted to polymerize propylene, having a normalboiling temperature of 47 C. in the liquid-phase and at a temperature of about C.,

" thane at .a pressure of' about 150 lbs. absolute provides a suitable refrigerant, -When polymerizing iso-butylene whose normal boiling point isv 8 C., or its homologues of even higher boiling points, superatmospheric pressures may be applied advantageously. -P'olymerizing under pressure permits the use of cooling liquids having much lower boiling points than the olefines, and large differences in boiling points between oleflnes and refrigerant prevent substantial losses-'of oleiines during the vaporization of the refrigerant.v

In practice the mixture of olenes and cooling liquid is preferably chilled to approximately the correct reaction temperature and is kept under sufficient pressure, to insure its being in the liquid phase. A catalyst is added or the liquid is introduced into the vessel containing a catalyst,

to allow the polymerization reaction to take place.`

During the reaction the pressure may be regulated to maintain the desired temperature. Stirring means may be provided to keep the mass agitated for the purpose of causing quick and complete contact between catalyst and olenes.

When polymerizing in the presence of a gaseous catalyst,such as boron fluoride, the oleilnes may be sprayed into an atmosphere containing the catalyst, and the cooling liquid is injected into the reaction zone either separately or in solution of the oleflnes. 'I'he spraying method has severalA great advantages over the method in which a pool of reacting masses is maintained. Evapora- Ico tion of the cooling liquid can proceed at a greatly increased rate and the dissipation of heat due to the greatly increased contact surface may become in the reaction at any one time must be relativelyl small,` and the total replaced by other cooling methods described below. y J

Practical 'tests have proven Athat when spraying -flnely divided oleflnes either in the liquid or gase- .ous form in contact with the catalyst in the absence of a self-evaporating cooling agent against a cold solid surface -in the presence of a suitable' solvent,or into a moving streamof a suitable cold solvent, very favorable results maybe o b-A tained, the solvent serving to keep the product of.v

vreaction in the liquid state for the purpose of removal. Concentrates of oleflnes containing 80% and. more of active' components can be polymerv ized without danger of incomplete polymerization, oleiine concentrates containing more than 80% active components occasionally.v yielding products of higher molecular Weights than are obtainable from dilute lsolutions of olenes. Cooling liquid admixed to a concentrate can be so vproportioned to leave afterits vaporization a re- A action product containing 80% or more of polymers, and 'solvents to carry oi the product can be added after the reaction is substantially finished. y

Continuous operation ofthe process is facilitated by spraying, the ne division of the oleilnes allowing for immediate contact with the'cat'alyst thereby shortening the time of reaction and reducing delay and induction periods.

The spraying method also permits for the rpoly-k merization of gaseous oleflnes in the presence of gaseous catalysts, the cooling agent, if used, being the only liquid introduced into the reaction zone.l

Suitable cooling agents comprise `inert liquids, whose critical conditions are well above the temperatures and pressures of `the reactionzone, and whose boiling range under suitable pressures is 'within or slightly below the desired range of the reaction temperature. Most of them are normally gaseous and include compounds suchA as ethane, propane, overhead vapors from natural gasoline stabilization containingmostly ethane and propane, monochlor methane, diiluor-dichlor methane, etc., and .their mixtures.

Thequantities of cooling agent required to maintain the proper temperature cannot be accurately specified. It is desirable tovhave at least enough of it present to prevent the temperature at any timeduring the reaction from going above thev desired reaction temperature, which inthe case of polymerizing iso-butylene with boron ilu- .amount of cooling liquid should be sufficient so that the latent heat available by its vaporization is at least as great as the heat of polymerization.

In order to make the process continuous it is necessary that a suitable solvent or non-solvent carrier liquid carry away the products of polymerization from solid surfaces in or around the reaction zone. If a solvent for polymers is used, it may be incorporated into the `oleilnes prior to polymerization, or it may take the form of a scrubbing liquid which continuously washes the surfaces touched by the polymers, or else it may form a pool into which the polymers fall. Many of the cooling agents also act as good solvents for the polymers, and an excessof cooling agent may well serve to keep the polymers in the liquid form. Hydrocarbons such as propane, pentanes, naphtha, or substituted productsvof the type of carbon tetrachloride,chloroform, dichlorethane, etc. are good solvents for the purpose.

Carrier liquids of no or little solvent effect on polymers, such as acetone, other lowerketones and lower mono-alcohols, glycols, certain esters,

4oride is of the order of 30 C. In any event the from the polymers by evaporation, either before or after the polymers are blended with other hydrocarbon oils, such as lubricating oil. i

The products of polymerization, if produced according to our invention, contain substantial amounts of components having molecular weights. in excess of 10,000. These high molecular weight substances are no longer viscous 'sticky fluids like the lower homologous members ofthe group but are elastic, rubbery materials.

In Figure 1, one possible form of carrying out the process of this invention is shown which enables the continuous production of olefine polymers in contact with a gaseous catalyst by spraying liquid olenes mixed with a cooling agent into an atmosphere containing the catalyst. Figure `2 represents a variation of the process of Figure 1, in which gaseous olenes are injected Vinto the catalyst in the presence of a spray of cooling agent,

Referring to Figure l: Iso-butylene or any of the suitable 'olefines previously described is introduced into the system from a source not shown, through line I. As it proceeds to chilled coils 2, it is mixed in a T 3 with liquid propane or other suitable cooling agent. The mixture is cooled in a chiller 2 to about -50 C., and is then released through a valve 4 and a spray nozzle 5 into a reactor 6. l

Instead of a spray nozzle, which at times may have a tendency to clog, a rapidly rotating plate can be employed onto which the liquid mixture drops after beingdischarged from the pipe line I. The liquid is immediately thrown 01T in the form of a fine spray.

Boron fluoride, or its equivalent, alone or in dilution. of an inert gas, is introduced through a line 1, 'a blower 8 and a line 9 into the reactor 6.

The reactor 6 is a tall cylindrical vessel, preferably With a cone bottom. The discharge end of the line 9 may be tangentially disposed in relation to the reactor 6, so as to impart to the boron fluoride-bearing gas in the reactor a vrotating motion. The spray of iso-butylene and propane from nozzle 5 descends as a fine rain in countercurrent to the ascending boron fluoride. As the gfiso-butylene polymerizes, heat is developed and evaporation of propane occurs, which keeps the temperature rslightly below 30 C. The height of the reaction vessel is so chosen as to permit for enough time of reaction to substantially polymerize the iso-butylene during its descent. The time of .reaction depends a great deal on temperature, purity of iso-butylene and condition of boron fluoride. The presence of small quantities of hydrogen 'fluoride moisture or other impurities in/the boron fluoride may greatly accelerate the polymerization reaction.

` Propane vapors containing boron fluoride are withdrawn from reactor 6 through a -reux line I0 at the top of the reactor. 'I'hey pass through a scrubber II in countercurrent to a vsuitable solvent for polymers, such as pentanes, which descends through the reflux line and `flows downward in a hn on the inside wall of the reactor. Means, such as a trough ordistributor 31, may be provided to distribute the film ofV descending pentanes over the entire wall area,-which positively prevents accumulation of polymers and plugging of the reactor. Likewise the scrubber and the reflux line are continuously washed and freed 'from depositing polymers. s f

The relative position of the iso-butylene in take and. reux line is of some importance.l In

order to prevent the escape of a substantial portion of unreacted vaporized iso-butylene into the reux line and scrubber, the reflux line is preferably connected to the reactor at a pointA to chilled coils I2 and thence to a separator I3.V

Propane is liquefied, separated from gases containing boron fluoride, and is pumped by a pump I4 to aT 3, in which itis mixed with fresh iso-butylene. Part or all of thel propane may be diverted through line I5 and be sprayed into the reactor 6 at one or several convenient points.

A solvent, such as pentane, which' ows downward on the inside wall of the reactor 6 accumulates in the cone-bottom I6 to form a pool. Iso-butylene polymers descending through the atmosphere of boron fluoride, are taken up in the pool and dissolved. At times it may be desirable to heat `the liquid in the pool to accelerate the rate of dissolving polymers and to reduce the viscosity of the resulting solution. This can be achieved by means of a heating coil 36. To provide agitation and to promotefurther po-lymerization of a small portion ofvunrezted or only partly polymerized iso-butylene, a gas containing some boron fluoride may be blown through the solution by means of line I'I. If desired all of the make-up boron fluoride may be introduced atthis point, in which case, the valve inline 9 is closed. The gaseous boron fluoride rises immediately to the surface of the pool and into the gaseous space of the reactor 6.

The solution of polymers is continuously withdrawn from the reactor 6 by a pump I8, which forces it through a coil I9 in a furnace 20. A

,light high-grade neutral oil may be introduced into the stream of the polymer' solution in a T .2I which is preferably located between the pump l I8 and the coil I9. The mixture, after passage through the coil I 9, is introduced into a fractionator 22, from which small amounts of propane plus some boron fluoride are taken overhead as vapors; the solvent is removed as a liquid side stream, if desired, and polymers, dissolved in the neutral oil, are withdrawn as a bottom stream. The vapors from the fractionator passing through a conduit 23, join the vapors from Vthe scrubber II at a point 24, and flow together to the chilled coils I2. The separated solvent is cooled in a cooler and goes into a storage tank 26. y The pump 2 1 conveys it from storage tothe top of the scrubber II through a line 28, ordirectly into the cone-bottom I6 of the reactor 6 through av line 29. Instead of pentanes, other solvents for polymers of suitable boiling range can( be employed, such as benzene, carbon tetrachloride, chloroform, dichlorethane, etc.

The mixture of polymers.I separated in the Vstorage through a line Jil.

fractionator Il, goes from the fractionator to Boron nuoride taken from the top of the separator i8 may be returned to thereaction zone by means of thev blower l, either directly through a line 3l, or by wayof a purifier 32 and lines I3 land 84. maybe drawn off through valved line Ii. l

It may at times be useful to shorten theA delay or induction period preceding. the .polymerization by introducing a trace of boron fluoride into the liquid stream of iso-butylene at a point aheadl of the reactor. Usually thepropane issuing from lthe separator Il contains traces vof boron fluoride, which materially reduces the induction period. The contamination of the cooling agent with the catalyst may even .be large enough to` necessitate placing the vmixing T l past the chilled coils 2 rather` than ahead of it, as shown in the drawings, in order to avoid excessive prel polymerization in the coils and plugging of the spray device. l v

If polymerization is to be carried out by spraying polymerizable oleilnes against a cold surface in the absence of a cooling agent, the wall of the reaction vessel 6 may be chilled from the out-- side. for instance, by providing a jacket and evaporating therein a suitable refrigerant. A quantity of solvent for polymers may be added to the olehnes, provided this does not interfere with the formation of the desired rubbery, elastic polymers, said quantity being large enough to keep t'he product of polymerization4 in sufilciently liquid state to allow its flowing down the wall. 'I'he scrubber Il may in this case be eliminated since there are very small quantities of ascending vapors capable of carrying unreacted oleilnes and the probability. of clogging the vapor exit line is verysmall.

When polymerizing gaseous iso-olenes, a'reac-v torarra'nged as shown in Figure 2 may be used.

Boron uoride and iso-olennes are introduced through .lines 44 and 45, respectively, into the lower part of a reactor 43, in such a manner that substantially instantaneous mixing in the reactor takes place. Cooling, liquid is sprayed through a line 30 and an atomizer Il into the upper part of the reactor 43. The spray of cooling liquid descends in countercurrent to the rising mixture of oleflne and boron fluoride gases. As polymerization occurs, cooling liquid evaporates and rises while non-vaporous polymers fall downward into a pool 40 consisting of pentanes or the like in the bottom of the reactor 43. Vapors consisting of :Loslassenv cooling agent, unreacted iso-oleilnes and' boron 'fluoride are withdrawn through reflux line and are scrubbed inlscrubber 42 by vthe descending pentanes.

The pressure yin the reaction vessel may be v varied to suit conditions, higher pressure accelerating the polymerization and raising the vboiling range of a givenL coolingl agent.

While the type of apparatus described is particularly suited for the polymerization of liquids and gases in the presence of gaseous catalysts, it shall be understood that other'types of apparatus applicable to the use of liquid and solid catalysts can be designed. We do not intend to'limit our invention to any particular apparatus, the only limitations of our invention being those disclosed in the following-claims.

We claim as our invention:

l. In the process of polymerizing tertiary base olefines of less than 9 carbon atoms by treating same with an active nuoride to produce rubberlike polymers, the improvement comprising form,- ing a liquid solution of the ole'nes in an inert lower-boiling liquid hydrocarbon solvent for the olenes, the solvent having a boiling temperature at the operating `pressure of the polymerization zone which substantially corresponds to the desired treating temperature land -is below the boiling temperature of the oleflnes, injecting the solution ina state oftlne division into the reaction zone containing a gaseous catalyst of the group consisting of boron uoride and hydrogen uoride, to effect polymerization of the oleflnes, whereby heat is liberated and the liquid solvent is vaporized, and maintaining an excess of the liquid solvent in the solution entering the polymerization zone over the quantity of the solvent which is evaporated due to the heat of reaction.

. 2. 'I'he process of claim l in which the olenes are substantially in the liquid state during polymerization.

' 3. 'Ihe process of claim 1 in which the surface of the reaction zone is continually washed with an organic liquid having a greater wetting power for the surface than the products of the polymerization.

4. 'Ihe process of claim. 1 in which the surface of the reaction zone is continually washed with a lower' ketone of the type vof acetone.

5. The process of'claim 1 in which the surface of the reaction zone is continually washed with asolvent for theproducts of the polymerization.

MARTIN n: sm. -mEDEmcK B. mmm. 

